Tabell, Victor Oliver. Partial Molar Volume.

Page 1 of 5

Calculation of Partial Molar Volumes of NaCl Solutions at Varying
Concentrations

V.O.L.Tabell

Department of Mining, Metallurgical and Materials Engineering
University of the Philippines, Diliman
vo_tabell@yahoo.com
Abstract
This paper discusses the method in computing for the partial molar volume of a NaCl solution
at varying concentrations from 1.5M to 0.09375M. Partial molar volume is the change in the
volume of a solution when a mole of one or more of its component is added. The experiment
showed that for NaCl solutions at constant room temperature, the partial molar volume of the
solvent, which was water, increases as the partial molar volume of the solute decreases. This was
mainly due to the solute-solute and solute-solvent interactions within the solution. The values
calculated for the solvent approached the literature value for pure water, but the values for the
solute did not approach the literature value of NaCl solutions at infinite dilutions. The
discrepancy might have been due to some systematic errors in the experiment. Nonetheless, if the
proper execution of the methodology is done, the partial molar volumes for the solute might be
corrected.

1. Introduction
Knowledge of various solute-solvent and solute-
solute interactions is very important to understand
various fundamental phenomena. In addition to the
scientific interest, mixing volume effects are
important from both theoretical and practical point of
view. Partial molar volumes and especially their
values at infinite dilution are useful in examination of
ion-ion and ion-water interactions [1].
By examining the apparent molar volumes and
partial molar volumes of solutes as a function of size,
nature, temperature and composition of mixed
solvent it is possible to study the effect of these
parameters [1].
For a binary system with components 1 and 2, the
partial molar volume of component 1 is given by:

(Eq. 1)
Where V is the total volume, n1 is the number of
moles of 1. Partial molar volume of 1 is, therefore,
the change in volume per mole of 1 added when an
infinitesimal amount of 1 is added to the solution at
constant P and T [2].
The total volume of the binary solution is
determined by adding the amounts of each
component.

(Eq. 2)
where V
1
and V
2
are partial molar volumes of
components 1 and 2 respectively.
The total volume of an amount of solution
containing 1 kg of water (18.0153g/mol) and m mole
of solute is given by [3]

(Eq. 3)

Let V
1
0

be the molar volume of pure water
equivalent to 18.016/0.997044 = 18.069 cm
3
/mol at
25C. Then we define the apparent molar volume, ,
of the solute by the equation [3]

(Eq. 4)
By considering the densities of the solution and the
pure solvent and the molecular weight of the solute,
apparent molar volume, , can be expressed as [3]
Tabell, Victor Oliver. Partial Molar Volume. Page 2 of 5

(

|
|
.
|

\
|

=
e
W W
W W
m
MW
d
0
0
*
1000 1
|
(Eq. 5)


where W = weight of pycnometer filled to mark with
solution
W
0
= weight of pycnometer filled to mark
with pure water
W
e

W
= weight of empty pycnometer

MW = molecular weight of solute
d = density of the solution

The molality m of each solution is computed using
the formula
|
.
|

\
|
|
.
|

\
|
=
1000
_
1
2
M
M
d
m
(Eq. 6)

where d = density of the solution (g/cm
3
)
M = molarity of the solution (mol/L)
M
2
= molecular weight of the solute (g/mol)
According to the Debye-Huckel theory for dilute
solutions, for solutions of simple electrolytes, it has
been found that many apparent molar quantities such
as vary linearly with [3].

We obtain

(Eq. 7)

(Eq. 8)

where
0
= apparent molar volume extrapolated to
zero concentration
V
1
0
= 18.069 cm
3
/mol

The objective of the experiment is to analyze the
partial molar volumes of NaCl and water in varying
concentrations of the salt solution.
2. Methodology
The experiment made use of a pycnometer to
acquire a definite volume of liquid, for the density
computations. The pycnometer was first rinsed using
acetone and heated in the oven for 10 minutes until
the inside has dried up. The weight of the pycnometer
was determined after drying. It was oven dried and
weighed again until the weight difference was 0.01g.

The pycnometer was calibrated by filling it with
deionized water then covering it with the capillary
stopper. The pycnometer was set in a water bath at
constant temperature of 25C. At thermostat, it was
removed from the bath and water around the surface
and on the openings of the capillary stopper was
wiped off, and then weighed. This was done three
times.

After calibration, the preparation of NaCl solution
was done. A 1.5M NaCl solution was prepared by
computing the needed weight of the NaCl crystals
and diluting it in a 200mL volumetric flask. The
solution was poured into the pycnometer after rinsing
it with an aliquot. Similar to the previous step, the
pycnometer was again placed in a water bath to reach
thermostat. At thermostat, it was removed from the
bath, wiped off, and then weighed. This too was done
three times.

The NaCl solution was then diluted into a 0.75M
solution, and the same weighing procedure was done.
The dilution and weighing continued for 0.375M,
0.1875M and 0.09375M NaCl solutions.
3. Results and Discussion
The pycnometer was calibrated in order to
determine the volume of the liquid it can contain. The
three recorded weights of the pycnometer filled with
water were averaged; the weight of the empty
pycnometer was subtracted to the averaged weight;
and the difference was divided to the density of pure
water at 25C, 0.997044g/mL [4]. These are all
shown in Table 1.

Table 1.
Averaged weights of pycnometer +
water
46.59827 g
Weight of empty pycnometer 21.60810 g
Weight of water in pycnometer 24.99017 g
Equivalent volume of water 25.06426 mL

The densities of the NaCl solutions were computed
by averaging the three recorded weights of each
Tabell, Victor Oliver. Partial Molar Volume. Page 3 of 5

solution; subtracting the averaged weight to the
weight of the empty pycnometer and dividing the
difference to the previously computed volume,
25.06426mL. Refer to Table 2 for computed densities.
The values of apparent molar volume, , and
molarity, m, were calculated using Equations 5 and 6
(refer to Appendix for computed values). The and
m values were graphed and the trend line was used
to calculate the slope d/dm and to solve the value
of the zero concentration
0
, which is the y-intercept.


Figure 1.

From Figure 1, the computed slope of the line was
11.26 and the apparent molar volume at zero
concentration was 6.9327. These values were used
for the compute the partial molar volumes of the
solute NaCl and the solvent water as used in
Equations 7 and 8.
The tabulated values of the computed V
1
and V
2

are shown in Table 2.

Table 2.
M
(mol/L)
m
(kg/mol)
d
(g/mL)
V1
(mL/mol)
V2
(mL/mol)
1.5 1.549425 1.055761 17.87 27.96
0.75 0.762497 1.027441 18 21.68
0.375 0.378385 1.012968 18.06 17.32
0.1875 0.188511 1.005594 18.06 14.27
0.09375 0.094094 1.00182 18.07 12.11

From the table, the computed partial molar
volumes of the solute, V
2
, showed a decreasing trend;
while the partial molar volumes of the solvent, V
1
,
showed the opposite. It was noticed that as the
concentration of the NaCl solution approached zero,
V
1
approached the theoretical partial molar volume of
pure water which was 18.069 mL/mol.
V
2
on the other hand, was not able to approach the
theoretical partial molar volume value of NaCl at
infinite dilution of water, 16.624 mL/mol [5]. It has
gone lower than it, reaching a value of 12.11 mL/mol
which signifies errors done in the experiment.
The computed densities of the NaCl solutions were
supposed to be compared to literature density values
of NaCl solution and for this, the percent weight of
NaCl in each of the solution was needed; however,
the obtained list of values only had whole numbers
for percent weights, hence interpolation was done in
order to compute for the exact density values. A plot
was made from the percent weights and literature
density values prior to the interpolation to check if
the trend of the plot was linear. The resulting r
2
value
was 0.9994, thus proving that the interpolation was
valid (see Appendix for this). The computed percent
weights, errors and interpolated literature density
values are shown in Table 3.

Table 3. [6]
Percent
weight
of NaCl in
soln
Literature
density values
Computed
Density
(g/mL)
Percent
error
32.76% 1.2433 1.055761 15.08%
16.45% 1.1193 1.027441 8.207%
8.284% 1.0573 1.012968 4.193%
4.138% 1.0257 1.005594 1.960%
2.067% 1.0100 1.00182 0.810%

From the range of errors computed, some of the
values were very small, especially for the very
diluted solution, and high percent errors for the
highest concentration. Another observation was the
increasing trend of error from the lowest
concentration up to the highest concentration.
Systematic errors could be a possible reason for this.
The test replicates done for the weighing of the
pycnometer for every concentration might have
caused the average to be too high or too low, instead
of being normalized. This causes the error to be high
especially in the higher concentrations since more
NaCl was used. Nonetheless, errors in preparing the
y = 11.26x + 6.9327
R = 0.7976
5
9
13
17
21
25
0.2 0.7 1.2 1.7
A
p
p
a
r
e
n
t

m
o
l
a
r

v
o
l
u
m
e

Square root of molality
Tabell, Victor Oliver. Partial Molar Volume. Page 4 of 5

sample and conducting the experiment, might also be
a major reason for the wide range of errors.
4. Conclusion

The experiment showed that for NaCl solutions at
constant room temperature, the partial molar volume
of the solvent, which was water, increases as the
partial molar volume of the solute decreases. This
was mainly due to the solute-solute and solute-
solvent interactions within the solution.
The computed partial molar volume value of water
in the solution approached the partial molar volume
of pure water at concentration approaching zero.
However, the partial molar volume of NaCl in the
solution did not approach the theoretical partial molar
volume of NaCl at infinite dilution, but went lower it
instead. This must have been due to systematic errors
in the experiment.

The experiment yielded density errors ranging
from 0.810% to 15.08%. This could have affected the
calculations of the partial molar volumes.

References
[1] Sahayaamutha, P. "Partial molar volumes of
transfer of some biologically important compounds
from water to aqueous sodium chloride and
potassium chloride solutions at 308 & 318K."
Oriental Journal of Chemistry. (2010): n. page. Web.
24 Jan. 2013.

[2] "EXPERIMENT 5 - DETERMINATION OF
PARTIAL MOLAR QUANTITIES." n. page. Web.
24 Jan. 2013.
<https://docs.google.com/viewer?a=v&q=cache:
pDBnjDgxrpkJ:www.chem.boun.edu.tr/webpages/co
urses/chem356/EXP5procedure.pdf
&hl=en&gl=ph&pid=bl&srcid=ADGEEShTH6I6Nl
wTWjJauM1srnfGVjnfpkGPATB0f-
umsSIdoUDdmF2UD5FiZAd19hFGiaj4ffunOU0Z1s
bsSWtq8biYqpFN0zYQSzLVEet1ulYMM2iQ7jk42
S12RF76QUX73nCsW6ae&sig=AHIEtbQ-
OnMe_W2ZgEoA2TxqAmrH1G84NQ>.
[3] "Surface Tension Measurements Using the
Capillary Method." Trans. Array Laboratory Manual
in Metallurgical Thermodynamics. Quezon City:
Print.

[4] "Density of Water (g/cm3) at Temperatures from
0C (liquid state) to 30.9C by 0.1C inc.." n. page.
Web. 24 Jan. 2013.
<http://www.simetric.co.uk/si_water.htm>

[5] F.J. Millero. The Apparent and Partial Molal
Volume of Aqueous Sodium Chloride Solutions at
Various Temperatures. The Journal of Physical
Chemistry. (1969) 358.

[6] "Density of sodium chloride." n. page. Web. 24
Jan. 2013. <http://www.saltinstitute.org/About-
salt/Physical-properties>.

Appendix
Sample Calculations
i. Computation of the volume of
pycnometer
Volume = (46.59827 g - 21.60810 g) / 0.997044g/mL
Volume = 24.99017 g / 0.997044g/mL
Volume = 25.06426 mL

ii. Computation of molarity

|
.
|

\
|
|
.
|

\
|
=
1000
_
1
2
M
M
d
m


m = 1 / [(1.055761/1.5)-(58.44/1000)]
m = 1.549425

iii. Computation of apparent molar
volume
(

|
|
.
|

\
|

=
e
W W
W W
m
MW
d
0
0
*
1000 1
|

= 1/1.055761 [58.44-(1000/1.549425)
(48.0699746.59827/46.59827-21.6093)]
= 19.36031
Tabell, Victor Oliver. Partial Molar Volume. Page 5 of 5

iv. Table of computed molarity and
apparent molar volumes

m m
1.549425 1.244759 19.36031
0.762497 0.873211 17.97242
0.378385 0.61513 16.03051
0.188511 0.434179 12.88642
0.094094 0.306748 7.530128



v. Graph of %NaCl vs Literature Values
of Densities



y = 0.0076x + 0.9943
R = 0.9994
0.95
1
1.05
1.1
1.15
1.2
1.25
0 10 20 30